JP2020512471A - Flame-retardant polyamide molding material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant polyamide molding material. The plastic molding material comprises, in addition to at least one thermoplastic polyamide and glass fibers, a specific combination of at least three flame-retardant additives.

Description

  The present invention relates to a glass fiber-reinforced thermoplastic molding material based on polyamide and having flame retardant properties.

  Flame retardants for thermoplastic polymers are known per se. DE-A 19960671 describes conventional flame retardants such as phosphinates and melamine compounds.

  JP2014-152322 describes flame-retardant glass fiber-reinforced polyamide resins containing organic phosphinates, melamine polyphosphates and phosphazene compounds as flame-retardant additives. The molding materials mentioned in the examples are 55.0% by weight of glass fibers, 2.5-3.0% by weight of phosphazene compounds, 0.5-1.0% by weight of melamine polyphosphate, and 10.0. ˜15.0 wt% DEPAL. The molding composition according to Example 2 comprises 3.0% by weight PA6, 23.0% by weight PA66, 5.0% by weight PA6T / 6I, 10.0% by weight DEPAL, 1.0% by weight melamine poly. It contains phosphate, 3.0 wt% phosphazene compound, and 55.0 wt% glass fiber. The UL94 test results for 0.8 mm thick sheets are listed. The glow wire test was not performed.

  Such molding compounds pass the UL94 test for specimens with a thickness of 0.4 mm and 0.8 mm, but do not pass the glow wire test of real component parts, for example plugs with different wall thicknesses. Using the amount of phosphazene compound and melamine polyphosphate required to pass the component part test results in the undesired interaction of both components, resulting in a black coloration of the material and formation of volatile compounds, Machining into high quality component parts becomes impossible.

DE-A199960671 JP2014-152322

  The object of the present invention is to specify a flame-retardant input material, which leads to a glass fiber reinforced polyamide molding material, which not only meets the requirements of UL94 but also the glow wire test in various forms and can be processed without discoloration. Is to provide a mixture of.

（式中、ｍは３〜２５の整数であり、Ｒ^４及びＲ^４’は同一又は異なり、Ｃ_１〜Ｃ_２０−アルキル−、Ｃ_６〜Ｃ_３０−アリール−、Ｃ_６〜Ｃ_３０−アリールアルキル−、又はＣ_６〜Ｃ_３０−アルキル−置換アリールを表し、
ｎは３〜１０００を表し、Ｘは−Ｎ＝Ｐ（ＯＰｈ）_３又は−Ｎ＝Ｐ（Ｏ）ＯＰｈを表し、Ｙは−Ｐ（ＯＰｈ）_４又は−Ｐ（Ｏ）（ＯＰｈ）_２を表す）
の少なくとも１つのホスファゼン、
１．０〜６．０質量部の、成分Ｃとしての、リン酸又はポリリン酸の少なくとも１つの脂肪族又は芳香族エステル、
５．０〜３０．０質量部の、成分Ｄとしての、一般式（Ｉ）の少なくとも１つの金属ホスフィネート又はホスフィン酸塩、又は一般式（ＩＩ）のジホスフィン酸塩、又はそれらのポリマー、

（式中、
Ｒ^１、Ｒ^２は、同一又は異なり、水素、直鎖又は分岐のＣ_１〜Ｃ_６−アルキル、及び／又はアリールを表し；
Ｒ^３は、直鎖又は分岐のＣ_１〜Ｃ_１０−アルキレン、Ｃ_６〜Ｃ_１０−アリーレン、−アルキルアリーレン又は−アリールアルキレンを表し；
Ｍは、Ｍｇ、Ｃａ、Ａｌ、Ｓｂ、Ｓｎ、Ｇｅ、Ｔｉ、Ｚｎ、Ｆｅ、Ｚｒ、Ｃｅ、Ｂｉ、Ｓｒ、Ｍｎ、Ｌｉ、Ｎａ、Ｋ及び／又はプロトン化窒素塩基を表し；
ｍ＝１〜４；ｎ＝１〜４；ｘ＝１〜４、好ましくはｍ＝３、ｘ＝３である）
からなる混合物によって、達成される。 This object is according to the invention from 1.0 to 10.0, preferably from 2.0 to 6.0 parts by weight of the general formula (IX) or (X) as component B.

(Wherein, m is an integer of 3 to 25, ^{R 4} and ^{R 4} 'are identical or _{different, C} 1 _{~C 20} - alkyl _{-, C} 6 _{~C 30 -} aryl _{-, C} 6 _{~C 30 -} aryl alkyl -, or _C 6 _{-C 30} - alkyl - represents a substituted aryl,
n represents _{3 to} 1000, X represents -N = P (OPh) ₃ or -N = P (O) OPh, and Y represents -P (OPh) ₄ or -P (O) (OPh) ₂ . )
At least one phosphazene of,
1.0-6.0 parts by weight of at least one aliphatic or aromatic ester of phosphoric acid or polyphosphoric acid as component C,
5.0-30.0 parts by weight of at least one metal phosphinate or phosphinate of the general formula (I) or a diphosphinate salt of the general formula (II), or polymers thereof, as component D,

(In the formula,
R ¹ and R ² are the same or different and represent hydrogen, linear or branched C ₁ -C ₆ -alkyl, and / or aryl;
R ³ represents a linear or branched _C 1 _{-C 10} - _alkylene, C 6 _{-C 10} - arylene, - alkylarylene or - an aryl alkylene;
M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base;
m = 1-4; n = 1-4; x = 1-4, preferably m = 3, x = 3)
It is achieved by a mixture of

  The sum of all components B, C and D amounts to 100.0% by weight, so there are no other or further components or ingredients. The mixture consists of components B, C and D and is present. The invention also relates to the use of the mixture for imparting flame-retardant properties to glass fiber reinforced polyamide molding compositions.

（式中、ｍは３〜２５の整数であり、Ｒ^４及びＲ^４’は同一又は異なり、Ｃ_１〜Ｃ_２０−アルキル−、Ｃ_６〜Ｃ_３０−アリール−、Ｃ_６〜Ｃ_３０−アリールアルキル−、又はＣ_６〜Ｃ_３０−アルキル−置換アリール又は一般式（Ｘ）の直鎖ホスファゼンを表し、ｎは３〜１０００を表し、Ｘは−Ｎ＝Ｐ（ＯＰｈ）_３又は−Ｎ＝Ｐ（Ｏ）ＯＰｈを表し、Ｙは−Ｐ（ＯＰｈ）_４又は−Ｐ（Ｏ）（ＯＰｈ）_２を表す）の少なくとも１つのホスファゼン、
ｃ） １．０〜６．０質量％の、成分Ｃとしての、リン酸又はポリリン酸の少なくとも１つの脂肪族又は芳香族エステル、
ｄ） ５．０〜３０．０質量％の、成分Ｄとしての、一般式（Ｉ）の少なくとも１つの金属ホスフィネート又はホスフィン酸塩、又は一般式（ＩＩ）のジホスフィン酸塩、又はそれらのポリマー

（式中、
Ｒ^１、Ｒ^２は、同一又は異なり、水素、直鎖又は分岐のＣ_１〜Ｃ_６−アルキル、及び／又はアリールを表し；
Ｒ^３は、直鎖又は分岐のＣ_１〜Ｃ_１０−アルキレン、Ｃ_６〜Ｃ_１０−アリーレン、−アルキルアリーレン又は−アリールアルキレンを表し；
Ｍは、Ｍｇ、Ｃａ、Ａｌ、Ｓｂ、Ｓｎ、Ｇｅ、Ｔｉ、Ｚｎ、Ｆｅ、Ｚｒ、Ｃｅ、Ｂｉ、Ｓｒ、Ｍｎ、Ｌｉ、Ｎａ、Ｋ及び／又はプロトン化窒素塩基を表し；
ｍ＝１〜４；ｎ＝１〜４；ｘ＝１〜４、好ましくはｍ＝３、ｘ＝３である）、
ｅ） ２６．０〜６５．０質量％の、成分Ｅとしての、ガラス繊維、
ｆ） ０〜１０．０質量％の、成分Ｆとしての、さらなる助剤、
を含み、成分ＡからＥ全体の総計は１００．０質量％となる、
熱可塑性成形材料によって達成される。 This purpose also includes the following ingredients:
a) 25.0-64.5% by weight of at least one thermoplastic polyamide as component A,
b) 1.0-10.0 mass% of the general formula (IX) or (X) as component B.

(Wherein, m is an integer of 3 to 25, ^{R 4} and ^{R 4} 'are identical or _{different, C} 1 _{~C 20} - alkyl _{-, C} 6 _{~C 30 -} aryl _{-, C} 6 _{~C 30 -} aryl alkyl -, or _C 6 _{-C 30} - alkyl - represents straight-chain phosphazene substituted aryl or formula (X), n represents 3 to 1000, X is -N = P _{(OPh) 3} or -N = P (O) OPh, Y represents -P (OPh) ₄ or -P (O) (OPh) ₂ ), at least one phosphazene,
c) 1.0-6.0% by weight of at least one aliphatic or aromatic ester of phosphoric acid or polyphosphoric acid as component C,
d) 5.0 to 30.0% by weight of at least one metal phosphinate or phosphinate of the general formula (I) or a diphosphinate of the general formula (II), or polymers thereof, as component D.

(In the formula,
R ¹ and R ² are the same or different and represent hydrogen, linear or branched C ₁ -C ₆ -alkyl, and / or aryl;
R ³ represents a linear or branched _C 1 _{-C 10} - _alkylene, C 6 _{-C 10} - arylene, - alkylarylene or - an aryl alkylene;
M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base;
m = 1-4; n = 1-4; x = 1-4, preferably m = 3, x = 3),
e) 26.0 to 65.0% by weight of glass fibers as component E,
f) 0 to 10.0% by weight of further auxiliaries as component F,
And the total of components A to E is 100.0% by mass,
Achieved by a thermoplastic molding material.

  As explained below, it is preferred if neither the mixture according to the invention nor the molding material according to the invention is free of melamine polyphosphate (MPP).

  The purpose is also to use such thermoplastic molding materials for mixing raw materials to produce molded articles, fibers or films, by a method for producing such thermoplastic molding materials, such thermoplastic molding materials. It is achieved by moldings, fibers or films made of a material, and by methods of manufacturing moldings, fibers or films from this molding material by melting, extruding and subsequently molding a thermoplastic molding material.

  Further, when the content of the flame-retardant melamine compound exceeds 6.0% by mass, the UL94 test is no longer passed.

  According to one embodiment of the invention, the molding composition according to the invention does not contain melamine cyanurate. Preferably, the molding material of the present invention contains a flame-retardant melamine compound such as melamine polyphosphate and melamine cyanurate at a maximum of 5.0% by mass, more preferably at a maximum of 2.0% by mass, and specifically, Does not contain.

  According to the invention, in the thermoplastic molding material, a proportion of phosphazene of 2.0 to 8.0% by weight and at least one aliphatic or aromatic of 1.5 to 6.0% by weight of phosphoric acid or polyphosphoric acid. It has been found that the combination with the group ester can meet all the requirements of the glow wire test and the UL94 test and achieve a homogeneous material with a light hue. The proportion of glass fibers is at least 26.0% by weight.

  Only certain combinations of components B to D lead to an advantageous profile of properties as flame-retardant system, both component part test and UL94 test at 0.4 mm and 0.8 mm for molding compound / component part. (GWT).

  As a result of the component parts made of the thermoplastic molding composition according to the invention, the glow wire test can pass in real component parts without ignition, while at the same time the UL94 test also satisfies all wall thicknesses. Let In addition, the good mechanical properties of the molding material / the moldings produced from it are retained.

  The advantages of the mixtures used according to the invention are achieved in particular for molding compositions based on polyamides which contain at least 26.0% by weight, preferably at least 29.0% by weight and in particular at least 30.0% by weight of glass fibers.

  The individual components of the mixture used according to the invention and of the thermoplastic molding material are explained more particularly below.

  The proportions reported below are based on the total of components A to E, which add up to 100% by weight (independent of the presence of further components whose amount is also based on the sum of components A to E).

  The lower and upper limits stated individually for the individual components may be freely combined with one another. The subcombinations thus formed also form part of the subject matter of the invention.

  As component A, the thermoplastic molding material comprises 25.0 to 64.5% by weight, preferably 26.5 to 61.5% by weight, preferably 25.0 to 56.0% by weight, in particular 41. 0 to 52.0% by weight of at least one thermoplastic polyamide.

  The polyamide of the molding material according to the invention has a viscosity number of generally 90 to 350, preferably 110 to 240 ml / g, measured according to ISO 307 at 25 ° C. with a 0.5% by weight solution in 96% by weight sulfuric acid. Have.

  Molecular weights of at least 5000, as described in, for example, U.S. Pat. Nos. 2,071,250, 20,712,51, 2,130,523, 2,130,948, 2,241,322, 2312966, 2512606, and 3,393,210 ( Semi-crystalline or amorphous resins having a mass average) are preferred.

  Examples include polyamides derived from lactams having 7 to 13 ring members such as polycaprolactam, polycaprylolactam and polylaurolactam, and polyamides obtained by reacting dicarboxylic acids with diamines.

  Useful dicarboxylic acids are alkanedicarboxylic acids having 6 to 12, in particular 6 to 10 carbon atoms, and aromatic dicarboxylic acids. Here, as the acid, only adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid and / or isophthalic acid may be mentioned.

  Particularly suitable diamines are alkanediamines having 6 to 12, in particular 6 to 8 carbon atoms, and m-xylylenediamine, di (4-aminophenyl) methane, di (4-aminocyclohexyl) methane, It is 2,2-di (4-aminophenyl) propane, 2,2-di (4-aminocyclohexyl) propane, or 1,5-diamino-2-methylpentane.

  Preferred polyamides are polyhexamethylene adipamide, polyhexamethylene sebacamide, polycaprolactam, and especially nylon-6 / 66 copolyamides with a proportion of caprolactam units of 5 to 95% by weight.

  Further suitable polyamides can be obtained from ω-aminoalkyl nitrites, for example from aminocapronitrile (PA6) and adiponitrile and hexamethylenediamine (PA66), by so-called direct polymerization in the presence of water, for example It can be obtained as described in DE-A 103 13 681, EP-A 1198491 and EP 922605.

  Also included are, for example, polyamides (polyamide-4, 6) obtainable by condensation of 1,4-diaminobutane with adipic acid at high temperature. A method for producing a polyamide having this structure is described in, for example, EP-A38094, EP-A38582 and EP-A039524.

  Also suitable are polyamides obtainable by copolymerization of two or more of the abovementioned monomers, or mixtures of polyamides mixed in any desired ratio.

  Furthermore, semi-aromatic copolyamides such as PA6 / 6T and PA66 / 6T with a triamine content of preferably less than 0.5% by weight, preferably less than 0.3% by weight, have proven suitable. (See EP-A299444 and EP-A667367).

Suitable copolyamides are:
A1) 20.0-90.0% by weight of units derived from terephthalic acid and hexamethylenediamine,
A2) 0-50.0% by weight of units derived from ε-caprolactam,
A3) 0-80.0% by weight of units derived from adipic acid and hexamethylenediamine,
A4) 0-40.0% by weight of further polyamide-forming monomers,
And the proportion of component (A2) or (A3) or (A4) or a mixture thereof is at least 10.0% by weight.

  Component A1) comprises from 20.0 to 90.0% by weight of units derived from terephthalic acid and hexamethylenediamine.

  In addition to units derived from terephthalic acid and hexamethylenediamine, copolyamides are units derived from ε-caprolactam and / or units derived from adipic acid and hexamethylenediamine, and / or further polyamide-forming monomers. Optionally containing units derived from

  The aromatic dicarboxylic acid A4) contains 8 to 16 carbon atoms. Suitable aromatic dicarboxylic acids include, for example, isophthalic acid, substituted terephthalic acids and isophthalic acids such as 3-t-butylisophthalic acid, polycyclic dicarboxylic acids such as 4,4'- and 3,3'-diphenyldicarboxylic acids. Acid, 4,4′- and 3,3′-diphenylmethanedicarboxylic acid, 4,4′- and 3,3′-sulfodiphenylcarboxylic acid, 1,4- or 2,6-naphthalenedicarboxylic acid, phenoxyterephthalic acid Of these, isophthalic acid is particularly preferred.

  Further polyamide-forming monomers A4) are dicarboxylic acids having 4 to 16 carbon atoms, and aliphatic or cycloaliphatic diamines having 4 to 16 carbon atoms, and amino acids having 7 to 12 carbon atoms. It can be derived from a carboxylic acid / corresponding lactam. By way of example of suitable monomers of these types, only the following are mentioned here: Representatives of aliphatic dicarboxylic acids are suberic acid, azelaic acid and sebacic acid, and representatives of diamines are 1,4-butanediamine, 1,5-pentanediamine, piperazine, 4,4′-diaminodicyclohexylmethane, 2,2- ( 4,4′-diaminodicyclohexyl) propane and 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane or metaxylylenediamine, and lactam / aminocarboxylic acid representatives of caprolactam, enanthlactam, ω-aminoundecanoic acid And laurolactam.

  Suitable such copolyamides are described, inter alia, in DE-A-102009011668.

  The following non-exhaustive list contains the polyamides mentioned above and further polyamides within the meaning of the invention, and the monomers present.

AB polymer:
PA4 Pyrrolidone PA6 ε-Caprolactam PA7 Ethanolactam PA8 Caprylolactam PA9 9-Aminopelargonic Acid PA11 11-Aminoundecanoic Acid PA12 Laurolactam AA / BB Polymer:
PA46 tetramethylenediamine, adipic acid PA66 hexamethylenediamine, adipic acid PA69 hexamethylenediamine, azelaic acid PA610 hexamethylenediamine, sebacic acid PA612 hexamethylenediamine, decanedicarboxylic acid PA613 hexamethylenediamine, undecanedicarboxylic acid PA1212 1,12-dodecane Diamine, decanedicarboxylic acid PA1313 1,13-diaminotridecane, undecanedicarboxylic acid PA6T hexamethylenediamine, terephthalic acid PA MXD6 m-xylylenediamine, adipic acid AA / BB polymer:
PA6I Hexamethylenediamine, isophthalic acid PA6-3-T Trimethylhexamethylenediamine, terephthalic acid PA6 / 6T (see PA6 and PA6T)
PA6 / 66 (see PA6 and PA66)
PA6 / 12 (see PA6 and PA12)
PA66 / 6/610 (see PA66, PA6 and PA610)
PA6I / 6T (see PA61 and PA6T)
PAPACM12 diaminodicyclohexylmethane, laurolactam PA6I / 6T / PACMT PA6I / 6T + diaminodicyclohexylmethane, terephthalic acid PA6T / 6I / MACMT PA6I / 6T + dimethyldiaminocyclohexylmethane, terephthalic acid PA6T / 6I / MXDT PA6I / 6T + m-xylylenediamine PA12 / MACMI laurolactam, dimethyldiaminodicyclohexylmethane as terephthalic acid, isophthalic acid PA12 / MACMT laurolactam, dimethyldiaminodicyclohexylmethane, terephthalic acid PA PDA-T phenylenediamine, terephthalic acid

  Component A is preferably a blend of at least one aliphatic polyamide and at least one semi-aromatic or aromatic polyamide.

  Particularly preferably used according to the invention as component A are polyamide-6 and polyamide-6.6 and optionally mixtures containing polyamide-6I / 6T. It is preferred to use polyamide 6.6 in a major amount. The amount of polyamide-6 is preferably 5.0-50.0% by weight, particularly preferably 10.0-30.0% by weight, based on the amount of polyamide-6.6. When polyamide-6I / 6T is used in combination, the proportion thereof is preferably 10.0 to 25.0% by mass, particularly preferably 0 to 25.0% by mass, based on the amount of polyamide-6.6.

  In addition to or instead of polyamide-6I / 6T, polyamide-6I or polyamide-6T or mixtures thereof may also be used.

  As component B, the thermoplastic molding material is preferably 1.0 to 10.0% by weight, preferably 2.0 to 6.0, in particular 3.0 to 5.0% by weight, of the general formula (IX). Alternatively, it contains at least one phosphazene of (X).

  The minimum amount of component B is at least 1.0% by weight, preferably 2.0% by weight and especially 3.0% by weight.

  The maximum amount of component B is 10.0% by weight, preferably 6.0% by weight, particularly preferably 5.0% by weight.

（式中、ｍは３〜２５の整数であり、Ｒ^４及びＲ^４’は同一又は異なり、Ｃ_１〜Ｃ_２０−アルキル−、Ｃ_６〜Ｃ_３０−アリール−、Ｃ_６〜Ｃ_３０−アリールアルキル−、又はＣ_６〜Ｃ_３０−アルキル−置換アリールを表す）の環状ホスファゼン、又は一般式（Ｘ）

（式中、ｎは３〜１０００を表し、Ｘは−Ｎ＝Ｐ（ＯＰｈ）_３又は−Ｎ＝Ｐ（Ｏ）ＯＰｈを表し、Ｙは−Ｐ（ＯＰｈ）_４又は−Ｐ（Ｏ）（ＯＰｈ）_２を表す）の直鎖ホスファゼンを意味すると理解されるべきである。 “Phosphazene” means the general formula (IX)

(Wherein, m is an integer of 3 to 25, ^{R 4} and ^{R 4} 'are identical or _{different, C} 1 _{~C 20} - alkyl _{-, C} 6 _{~C 30 -} aryl _{-, C} 6 _{~C 30 -} aryl alkyl -, or _C 6 _{-C 30} - alkyl - cyclic phosphazene, or the general formula of the substituted aryl represents a) (X)

(In the formula, n represents _{3 to} 1000, X represents -N = P (OPh) ₃ or -N = P (O) OPh, and Y represents -P (OPh) ₄ or -P (O) (OPh. ) Representing ₂ ) is to be understood as meaning a linear phosphazene.

  The preparation of such phosphazenes is described in EP-A0945478.

の式Ｐ_３Ｎ_３Ｃ_３６の環状フェノキシホスファゼン、又は式（ＸＩＩ）

による直鎖フェノキシホスファゼンが特に好ましい。 Formula (XI)

A cyclic phenoxyphosphazene of formula P ₃ N ₃ C ₃₆ , or a compound of formula (XII)

The linear phenoxyphosphazene according to is particularly preferred.

  The phenyl radical can be optionally substituted. Phosphazene in this application is described in Mark, J. et al. A. Allcock, H .; R. , West, R .; , "Inorganic Polymers", Prentice Hall International, 1992, pp. 61-141.

Preferably used as component B is a cyclic phenoxyphosphazene having at least 3 phenoxyphosphazene units. Corresponding phenoxyphosphazenes are described, for example, in paragraphs [0051] to [0053] of US2010 / 0261818. In particular, reference may be made to formula (I) therein. Corresponding cyclic phenoxyphosphazenes are further described in EP-A-2100919, in particular paragraphs [0034] to [0038] thereof. The production may be carried out as described in paragraph [0041] of EP-A-2100919. In one embodiment of the present invention, the phenyl group of cyclic phenoxyphosphazene, C 1 _~ 4 _- may be substituted by an alkyl radical. It is preferred if pure phenyl radicals are involved.

For a further description of cyclic phosphazenes, reference may be made to Roemppp Chemie-Lexikon, 9th edition, keyword "phosphazene". The preparation is carried out, for example, via cyclophosphazenes, which can be obtained from PCl ₅ and NH ₄ Cl, the chlorine group of cyclic phosphazenes being replaced by phenoxy groups by reaction with phenol.

  Cyclic phenoxyphosphazene compounds are described, for example, in "Phosphorus-Nitrogen Compounds" (Academic Press, 1972), H.S. R. Allcock, and "Inorganic Polymers" (Prentice Hall International, Inc., 1992), J. Am. E. Mark, H.M. R. Allcock and R.C. It may be manufactured as described by West.

  Component B is preferably a mixture of cyclic phenoxyphosphazenes with 3 and 4 phenoxyphosphazene units. The mass ratio of the ring containing 3 phenoxyphosphazene units to the ring containing 4 phenoxyphosphazene units is preferably about 80:20. Larger rings of phenoxyphosphazene units may be present as well, but in smaller amounts. A suitable cyclic phenoxyphosphazene can be obtained from Fushimi Pharmaceutical Co., Ltd. under the name RAVITOR® FP-100. It is a dull white / yellowish solid with a melting point of 110 ° C., a phosphorus content of 13.4% and a nitrogen content of 6.0%. The proportion of rings containing 3 phenoxyphosphazene units is at least 80.0% by weight.

  As component C, the thermoplastic molding material is preferably 1.0 to 6.0% by weight, preferably 2.5 to 5.5% by weight, in particular 3.0 to 5.0% by weight, of phosphoric acid or polyphosphorus. It comprises at least one aliphatic or aromatic ester of an acid.

又は、

又は、

（式中、
Ｒ^１＝ Ｈ、メチル、エチル又はイソプロピルであるが、好ましくはＨであり、
ｎ＝ ０〜７の間であるが、好ましくは０であり、
Ｒ^２〜６＝ Ｈ、メチル、エチル又はイソプロピルであるが、好ましくはメチルであり、Ｒ^６は、好ましくはＲ^４及びＲ^５と同一であり、
ｍ＝ 同一であり得るが必ずしもその必要はなく、１、２、３、４及び５の間であるが、好ましくは２であり、
Ｒ”＝ Ｈ、メチル、エチル、又はシクロプロピルであり得るが、好ましくはメチル及びＨである）。 For this reason, particularly solid, non-migrating phosphates having a melting point between 70 ° C. and 150 ° C. are preferred. This results in easier metering of the product and significantly less movement to the molding material. Particularly preferred examples are commercially available phosphate esters, PX-200 (registered trademark) (CAS: 139189-30-3) of Daihachi Chemical Industry Co., Ltd., or Sol-DP of ICL-IP. (Registered trademark). Further phosphoric acid esters suitably substituted with phenyl groups can be considered if this achieves the preferred solubility range. The general structural formula is as follows, depending on the substitution pattern in the ortho or para positions on the aromatic ring:

Or

Or

(In the formula,
R ¹ = H, methyl, ethyl or isopropyl, but preferably H,
n = 0 to 7, but preferably 0,
R ^2-6 = H, methyl, ethyl or isopropyl, but preferably methyl, R ⁶ is preferably the same as R ⁴ and R ⁵ ,
m = might be the same but not necessarily, between 1, 2, 3, 4 and 5, but preferably 2;
R ″ = H, can be methyl, ethyl, or cyclopropyl, but is preferably methyl and H).

PX-200 may be mentioned as a specific example:

  Particularly preferred is the use of at least one aromatic ester of polyphosphoric acid. Such an aromatic polyphosphate can be obtained, for example, from Daihachi Chemical Industry Co., Ltd. under the name PX-200.

  As component D, the thermoplastic molding composition according to the invention comprises 5.0 to 30.0% by weight, preferably 10.0 to 25.0% by weight, in particular 12.0 to 20.0% by weight, for example about 16. It contains 0% by weight of at least one metal phosphinate or phosphinate described below.

  The minimum amount of component D is 5.0% by weight, preferably 10.0% by weight, especially 12.0% by weight.

  The maximum amount of component D is 30.0% by weight, preferably 25.0% by weight, particularly preferably 20.0% by weight.

  An example of a preferred flame retardant for component D is a metal phosphinate derived from hypophosphorous acid. For example, a metal salt of hypophosphorous acid having Mg, Ca, Al, or Zn as a metal can be used. Aluminum hypophosphite is particularly preferred here.

  Also suitable are phosphinates of formula (I) or / and diphosphinates of formula (II) or polymers thereof.

（式中、
Ｒ^１、Ｒ^２は、同一又は異なり、水素、直鎖又は分岐のＣ_１〜Ｃ_６−アルキル、及び／又はアリールを表し；
Ｒ^３は、直鎖又は分岐のＣ_１〜Ｃ_１０−アルキレン、Ｃ_６〜Ｃ_１０−アリーレン、−アルキルアリーレン又は−アリールアルキレンを表し；
Ｍは、Ｍｇ、Ｃａ、Ａｌ、Ｓｂ、Ｓｎ、Ｇｅ、Ｔｉ、Ｚｎ、Ｆｅ、Ｚｒ、Ｃｅ、Ｂｉ、 Ｓｒ、Ｍｎ、Ｌｉ、Ｎａ、Ｋ及び／又はプロトン化窒素塩基を表し；
ｍ＝１〜４；ｎ＝１〜４；ｘ＝１〜４、好ましくはｍ＝３、ｘ＝３である）。

(In the formula,
R ¹ and R ² are the same or different and represent hydrogen, linear or branched C ₁ -C ₆ -alkyl, and / or aryl;
R ³ represents a linear or branched _C 1 _{-C 10} - _alkylene, C 6 _{-C 10} - arylene, - alkylarylene or - an aryl alkylene;
M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base;
m = 1-4; n = 1-4; x = 1-4, preferably m = 3, x = 3).

Preferably, R ¹ and R ² are the same or different and represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.

Preferably R ³ is methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene, phenylene or naphthylene; methylphenylene, ethylphenylene, tert-. Butylphenylene, methylnaphthylene, ethylnaphthylene or tert-butylnaphthylene; represents phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene.

Particularly preferably, R ¹ and R ² are hydrogen, methyl, ethyl and M = Al, with Al hypophosphite being particularly preferred.

The production of phosphinates is preferably carried out by precipitating the corresponding metal salts from aqueous solution. However, the phosphinates may also be precipitated in the presence of inorganic metal oxides or sulphides (white pigments such as TiO ₂ , SnO ₂ , ZnO, ZnS, SiO ₂ ) suitable as support materials. This results in surface-modified pigments that can be used as laser-markable flame retardants for thermoplastic polyesters.

  It is preferable to use a metal salt of a substituted phosphinic acid. Here, one or two hydrogen atoms are replaced by phenyl, methyl, ethyl, propyl, isobutyl, isooctyl as compared to hypophosphorous acid, or the radical R′-CH—OH is replaced by R ′. -Replaced by hydrogen, phenyl, tolyl. The metal is preferably Mg, Ca, Al, Zn, Ti, Fe. Aluminum diethyl phosphinate (DEPAL) is particularly preferred.

  For a description of phosphinates or diphosphinates, reference may be made to DE-A 1996 067 1 and DE-A 4430932 and DE-A 1993 3901.

  As component E), the thermoplastic molding composition comprises 28.0 to 80.0% by weight, preferably 29.0 to 60.0% by weight, in particular 30.0 to 39.0% by weight of glass fibers.

  These may be conventional glass fibers which may be used in the form of endless fibers or chopped glass fibers. The fibers may be uncoated or coated, for example coated with a silane sizing agent.

  What can be used in combination as component F is 0 to 10.0% by weight, preferably 0 to 5.0% by weight, in particular 0 to 3.0% by weight, of further auxiliaries. This amount is based on the sum of components AE. When used in combination with further auxiliaries, their minimum amount is preferably 0.5% by weight, particularly preferably at least 1.0% by weight, in particular at least 1.5% by weight. The further auxiliaries can be further additives or processing auxiliaries.

Suitable are, for example, mineral fillers such as talc, magnesium hydroxide, wollastonite needles, lubricants such as ester waxes and oxidized polyethylene waxes, stabilizers such as antioxidants, light stabilizers, phenols, phosphites and Mention may be made of phosphonite or acid scavengers, nucleating agents, carbon black or pigments such as white pigments such as TiO ₂ , ZnO, ZrO ₂ , SnO ₂ , ZnS and the like.

  Further flame retardants are also considered as component F, for example halogen-containing flame retardants.

  Suitable halogen-containing flame retardants are preferably brominated compounds such as brominated diphenyl ether, brominated trimethylphenylindane (DSB FR1808), tetrabromobisphenol A and hexabromocyclododecane.

を有する臭素化されたオリゴカルボナート（Ｇｒｅａｔ Ｌａｋｅｓ社のＢＣ５２又はＢＣ５８）である。 Suitable flame retardants are preferably brominated compounds such as the structural formula:

Is a brominated oligocarbonate with BC52 or BC58 from Great Lakes.

を有する、ｎ＞４のポリペンタブロモベンジルアクリラートである（例えばＩＣＬ−ＩＰ社のＦＲ１０２５）。 Particularly suitable is the formula:

Is a polypentabromobenzyl acrylate having n> 4 (for example, FR1025 from ICL-IP).

を有する、テトラブロモビスフェノールＡとエポキシドとのオリゴマー反応生成物（ｎ＞３）（例えばＤＳＢ社のＦＲ２３００及び２４００）をさらに含む：
難燃剤として好ましく用いられる臭素化されたオリゴスチレンは、トルエン中の蒸気圧浸透圧法により測定して、３〜９０の間の、好ましくは５〜６０の間の平均重合度（数平均）を有する。環状オリゴマーも同様に適している。本発明の好ましい実施形態では、臭素化オリゴマースチレンは以下に示す式Ｉを有し、式中、Ｒは水素又は脂肪族ラジカル、特にアルキルラジカルを表し、例えばＣＨ_２又はＣ_２Ｈ_５であり、ｎは鎖ビルディングブロックの繰り返し数を表す。Ｒ^１は、Ｈか、或いは臭素か、或いは慣例的な遊離ラジカル形成剤の断片であり得る：

Preferred brominated compounds have the formula:

Further comprising an oligomeric reaction product (n> 3) of tetrabromobisphenol A with an epoxide (eg, FR2300 and 2400 from DSB):
The brominated oligostyrenes preferably used as flame retardants have an average degree of polymerization (number average) between 3 and 90, preferably between 5 and 60, measured by vapor pressure osmometry in toluene. . Cyclic oligomers are likewise suitable. In a preferred embodiment of the invention, the brominated oligomeric styrene has the formula I shown below, in which R represents hydrogen or an aliphatic radical, in particular an alkyl radical, such as CH ₂ or C ₂ H ₅ . n represents the number of repeating chain building blocks. R ¹ can be H, or bromine, or a fragment of a conventional free radical forming agent:

  The value n may be 1 to 88, preferably 3 to 58. The brominated oligostyrene contains 40.0 to 80.0% by weight, preferably 55.0 to 70.0% by weight of bromine. A product consisting mainly of polydibromostyrene is preferred. These substances are soluble without decomposition and are soluble in, for example, tetrahydrofuran. Said material is optionally aliphatic hydrogenated, such as is obtained by thermal polymerization of styrene (according to DT-OS 2537385), by ring bromination of styrene oligomers or by free radical oligomerization of suitable brominated styrenes. , Can be manufactured. The production of flame retardants can also be carried out by ionic oligomerization of styrene and subsequent bromination. The amount of brominated oligostyrene required to impart flame retardant properties to the polyamide depends on the bromine content. The bromine content in the molding composition according to the invention is 2.0 to 30.0% by weight, preferably 5.0 to 12.0% by weight.

  The brominated polystyrene according to the invention is typically obtained by the method described in EP-A047549.

  The brominated polystyrenes obtainable in this way and commercially available are predominantly ring-substituted tribrominated products. n '(see III) generally has a value of 125 to 1500, which corresponds to a molecular weight of 42,500 to 235,000, preferably 130,000 to 135,000.

  The bromine content (based on the content of ring-substituted bromine) is generally at least 50.0% by weight, preferably at least 60.0% by weight, in particular 65.0% by weight.

  Commercially available powdery products generally have a glass transition temperature of 160-200 ° C. and can be obtained, for example, from Albemarle under the name HP7010 and from Ferro Corporation under the name Pyrocheck PB68. it can.

  Mixtures of brominated oligostyrenes and brominated polystyrenes may also be used in the molding compositions according to the invention, the mixing ratios being freely selectable.

  Chlorine-containing flame retardants are also suitable, with decanolane plus from Oxychem being preferred.

  Suitable halogen containing flame retardants are preferably ring brominated polystyrene, brominated polybenzyl acrylate, brominated bisphenol A epoxide oligomers, or brominated bisphenol A polycarbonate.

  In one embodiment of the invention, halogen-containing flame retardants are not used in the thermoplastic molding material according to the invention.

  Flame-retardant melamine compounds suitable as component F in the present invention reduce flammability and affect fire behavior in a flame-retardant manner when added to glass fiber-filled polyamide molding compositions, which Is a melamine compound that provides improved properties in the UL94 test and the glow wire test.

  The melamine compound is selected, for example, from melamine borate, melamine phosphate, melamine sulfate, melamine pyrophosphate, melam, melem, melon or melamine cyanurate, or a mixture thereof.

の反応生成物である。 Preferentially suitable melamine cyanurates according to the invention are preferably equimolar amounts of melamine (formula I) and cyanuric acid or isocyanuric acid (formula Ia and Ib).

Is a reaction product of.

The reaction product is obtained, for example, by reaction of an aqueous solution of the starting compound at 90-100 ° C. The commercially available product is a white powder with an average particle size d _{50 of} 1.5-7 μm and a d ₉₉ value of less than ₅₀ μm.

  Further suitable compounds (often also described as salts or adducts) are melamine sulphates, melamines, melamine borates, oxalates, primary phosphates, secondary phosphates and secondary pyrophosphates, melamine neopentyl glycol borates. is there. According to the invention, the molding composition is preferably free from the polymer melamine phosphate (CAS number 56386-64-2 or 218768-84-4).

  It has an average degree of condensation number n between 20 and 200 and is selected from the group consisting of melamine, melam, melem, melon, ammeline, ammelide, 2-ureidomelamine, acetoguanamine, benzoguanamine and diaminophenyltriazine. 1,3,5-triazine content of 1,3,5-triazine compound is 1.1 to 2.0 mol of 1,3,5-triazine compound per 1 mol of phosphorus atom, melamine polyphosphate It should be understood to mean salt. Preferably, the n value of such salts is generally between 40 and 150 and the ratio of 1,3,5-triazine compound per mole of phosphorus atom is preferably between 1.2 and 1.8. Is. Furthermore, the pH of a 10% by weight aqueous slurry of the salt produced according to EP-B10995030 is generally above 4.5, preferably at least 5.0. The pH is typically determined by adding 25 g of salt and 225 g of clean water in a 300 ml beaker at 25 ° C., stirring the resulting aqueous slurry for 30 minutes and then measuring its pH. The above-mentioned n value and number average condensation degree can be determined by 31 P-solid state NMR. J. R. van Wazer, C.I. F. Callis, J .; Shoolery and R.H. Jones, J. Am. Chem. Soc, 78, 5715, 1956 discloses that the number of adjacent phosphate groups exhibits a unique chemical shift that allows a clear distinction between orthophosphate, pyrophosphate, and polyphosphate.

  Suitable guanidine salts are:

CAS number g carbonate 593-85-1
g primary cyanurate 70285-19-7
g primary phosphate 5423-22-3
g secondary phosphate 5423-23-4
g Primary Sulfate 646-34-4
g secondary sulfate 594-14-9
Guanidine pentaerythritol borate n. a.
Guanidine Neopentyl Glucol borate n. a.
And urea phosphate green 4861-19-2
Urea cyanurate 57517-11-0
Ammeline 645-92-1
Ammelido 645-93-2
Merem 1502-47-2
Melon 32518-77-7

  In the context of the present invention, “compound” should be understood to mean, for example, benzoguanamine itself and its adducts / salts, as well as its derivatives and adducts / salts substituted with nitrogen.

のトリス（ヒドロキシエチル）イソシアヌレート（ＴＨＥＩＣ）、又は任意に混合物中に互いに存在し得る芳香族カルボン酸Ａｒ（ＣＯＯＨ）_ｍとのその反応生成物も適しており、ここでＡｒは、単環、二環又は三環の芳香族六員環系であり、ｍは、２、３又は４である。 Further, ammonium polyphosphate (NH ₄ PO ₃ ) _n in which n is about 200 to 1000, preferably 600 to 800, and formula (IV)

Of tris (hydroxyethyl) isocyanurate (THEIC), or its reaction product with an aromatic carboxylic acid Ar (COOH) _m , which may optionally be present in a mixture with one another, wherein Ar is a monocycle, It is a bicyclic or tricyclic aromatic 6-membered ring system in which m is 2, 3 or 4.

  Examples of suitable carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, pyromellitic acid, melophanoic acid, prehnitic acid. acid), 1-naphthoic acid, 2-naphthoic acid, naphthalenedicarboxylic acid and anthracenecarboxylic acid.

  The production is carried out by the reaction of tris (hydroxyethyl) isocyanurate with an acid, an alkyl ester thereof or a halide thereof according to the method of EP-A584567.

Such reaction products are a mixture of optionally crosslinked monomers and oligomeric esters. The degree of oligomerization is typically 2 to about 100, preferably 2 to 20. Preference is given to using a mixture of THEIC, and / or its reaction products, with phosphorus-containing nitrogen compounds, in particular (NH ₄ PO ₃ ) _n or melamine pyrophosphate or polymeric melamine phosphate. Mixing ratio, for example, _(NH 4 _{PO 3) n} mixed ratio THEIC of preferably 90.0 to 50.0: 10.0 to 50.0, in particular 80.0 to 50.0: 50.0 to 20 0.0 (mass% is based on a mixture of such components B1).

（式中、Ｒ、Ｒ’は、１〜１０個の炭素原子を有する直鎖状又は分岐鎖状アルキルラジカル、好ましくは水素を表す）のベンゾグアニジン化合物、及び特にリン酸、ホウ酸及び／又はピロリン酸とのそれらの付加物も適している。 Also, the formula V

A benzoguanidine compound (wherein R and R ′ represent a linear or branched alkyl radical having 1 to 10 carbon atoms, preferably hydrogen), and in particular phosphoric acid, boric acid and / or Also suitable are their adducts with pyrophosphate.

（式中、Ｒ、Ｒ’は、式Ｖで定義したとおりである）のアラントイン化合物、及びリン酸、ホウ酸及び／又はピロリン酸とのそれらの塩、及び式ＶＩＩ

（式中、Ｒは、式Ｖで定義したとおりである）のグリコルリル（glycolurils）又は上述の酸とのそれらの塩も、好ましい。 Also, the formula VI

An allantoin compound of the formula where R and R ′ are as defined in formula V, and salts thereof with phosphoric acid, boric acid and / or pyrophosphoric acid, and formula VII

Also preferred are glycololils of the formula where R is as defined in formula V or their salts with the acids mentioned above.

  Suitable products are commercially available or can be obtained according to DE-A19614424.

  The cyanoguanidines (formula VIII) that can be used according to the invention can be obtained, for example, by reacting calcium cyanamide with carbonic acid, the cyanamides produced dimerizing at pH 9-10 to give cyanoguanidines.

  The commercially available product is a white powder with a melting point of 209 ° C to 211 ° C.

  It is particularly preferred to use melamine cyanurate (eg Melapur® MC25 from BASF SE).

  In addition, it is possible to use separate metal oxides such as antimony trioxide, antimony pentoxide, sodium antimonate and similar metal oxides. However, it is preferred to avoid their use, since such metal oxides are already present in component B. Reference may be made to EP-A 0624626 for a description of pentabromobenzyl acrylate and antimony trioxide or antimony pentoxide.

  It is also possible to use phosphorus as component C, for example red phosphorus. Red phosphorus may be used, for example, in the form of a masterbatch.

（式中、
Ｒ^１〜Ｒ^４は、少なくとも１つのラジカルＲ^１〜Ｒ^４がハロゲンを表すという条件で、互いに独立してハロゲン又は水素を表し、
ｘ＝１〜３、好ましくは１、２であり、
ｍ＝１〜９、好ましくは１〜３、６、９、特に１〜３であり、
ｎ＝２〜３であり、
Ｍ＝アルカリ土類金属、Ｎｉ、Ｃｅ、Ｆｅ、Ｉｎ、Ｇａ、Ａｌ、Ｐｂ、Ｙ、Ｚｎ、Ｈｇである）
のジカルボン酸も考慮される。 Also, the formula

(In the formula,
R ^{1 to} R ⁴ each independently represent halogen or hydrogen, provided that at least one radical R ^{1 to} R ⁴ represents halogen.
x = 1 to 3, preferably 1, 2;
m = 1 to 9, preferably 1 to 3, 6, 9 and especially 1 to 3,
n = 2 to 3,
M = alkaline earth metal, Ni, Ce, Fe, In, Ga, Al, Pb, Y, Zn, Hg)
Other dicarboxylic acids are also considered.

Preferred dicarboxylic acid salts contain Cl or bromine or hydrogen as radicals R ^{1 to} R ⁴ , independently of one another, particularly preferably the radicals R ^{1 to} R ⁴ are all Cl or / and Br.

  The metal M is preferably Be, Mg, Ca, Sr, Ba, Al, Zn or Fe.

  Such dicarboxylic acid salts are commercially available or can be prepared by the method described in US Pat. No. 3,354,191.

  It is preferred not to use additional separate metal oxides or additional phosphorus or dicarboxylate salts.

  As the component F, a functional polymer can also be used. These can be, for example, flame-retardant polymers. Such polymers are described, for example, in US Pat. No. 8,314,202 and include 1,2-bis [4- (2-hydroxyethoxy) phenyl] ethanone repeat units. A more suitable functional polymer for increasing the amount of carbon residue is poly (2,6-dimethyl-1,4-phenylene oxide) (PPPO).

  It is preferred to use only flame retardant components B, C and D.

  Component F can also be an elastomeric polymer (often described as impact modifier, elastomer or rubber).

  Very generally, these are copolymers preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile, and 1 to 1 in the alcohol component. Acrylic acid ester or methacrylic acid ester having 18 carbon atoms.

  Such polymers are described, for example, in Houben-Weyl, Methoden der organischen Chemie, Volume 14/1 (Georg-Thieme-Verlag, Stuttgart, 1961), pages 392-406, and C.I. B. It is described by Bucknall in the monograph "Toughened Plastics" (Applied Science Publishers, London, 1977).

  Some preferred types of such elastomers are described below.

  A preferred class of elastomers are the so-called ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers.

  Generally, the EPM rubber is substantially free of double bonds, while the EPDM rubber has 1 to 20 double bonds per 100 carbon atoms.

  Diene monomers for EPDM rubbers include, for example, conjugated dienes such as isoprene and butadiene, and non-conjugated dienes having 5 to 25 carbon atoms such as penta-1,4-diene, hexa-1,4-diene, hexa. -1,5-diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene, and alkenylnorbornene, For example, 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodiene, such as 3-methyltricyclo [5.2.1]. 0.2.6] -3,8-decadiene and mixtures thereof. And the like. Hexa-1,5-diene, 5-ethylidene norbornene and dicyclopentadiene are preferred. The diene content of the EPDM rubber is preferably 0.5 to 50.0% by mass, in particular 1.0 to 8.0% by mass, based on the total mass of the rubber.

  EPM / EPDM rubbers can preferably be grafted with reactive carboxylic acids or their derivatives. Here, mention may be made, for example, of acrylic acid, methacrylic acid and its derivatives, such as glycidyl (meth) acrylate, and maleic anhydride.

（式中、Ｒ^１〜Ｒ^９は、水素又は１〜６個の炭素原子を有するアルキル基を表し、ｍは０〜２０の整数であり、ｇは０〜１０の整数であり、ｐは０〜５の整数である）
に適合するモノマーのモノマー混合物に加えることによって、好ましくはゴムに組み込まれる。 A further group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or esters of these acids. The rubber may further comprise dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids such as monomers containing esters and anhydrides and / or monomers containing epoxy groups. These monomers containing dicarboxylic acid derivatives / epoxy groups contain dicarboxylic acid / epoxy groups and have the general formula I or II or III or IV

(In the formula, R ^{1 to} R ⁹ represent hydrogen or an alkyl group having 1 to 6 carbon atoms, m is an integer of 0 to 20, g is an integer of 0 to 10, and p is 0. ~ Is an integer of 5)
Is preferably incorporated into the rubber by adding to the monomer mixture of monomers compatible with.

It is preferred if the radicals R ^{1 to} R ⁹ represent hydrogen, where m is 0 or 1 and g is 1. Corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.

  Preferred compounds of the formulas I, II and IV are maleic acid, maleic anhydride and esters of acrylic acid and / or methacrylic acid containing epoxy groups, for example glycidyl acrylate, glycidyl methacrylate, and esters with tertiary alcohols, For example, t-butyl acrylate and the like. The last-mentioned compounds do not have free carboxyl groups, but their behavior is close to that of free acids, so they are described as monomers with latent carboxyl groups.

  The copolymer is advantageously composed of 50 to 98% by weight of ethylene, 0.1 to 20.0% by weight of monomers containing epoxy groups and / or monomers containing (meth) acrylic acid and / or anhydride groups. The balance consists of (meth) acrylic acid ester.

Particularly preferably,
50.0-98.0, especially 55.0-95.0 mass% ethylene,
0.1 to 40.0, especially 0.3 to 20.0 mass% glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and 1.0 to 45.0, In particular, copolymers made from 10.0 to 40.0% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.

  Further preferred esters of acrylic acid and / or methacrylic acid are methyl, ethyl, propyl and i- / t-butyl esters.

  Furthermore, it is possible to use vinyl esters and vinyl ethers as comonomers.

  The ethylene copolymers described above can be produced by methods known per se, preferably by random copolymerization at elevated pressure and temperature. Corresponding methods are generally known.

  Preferred elastomers also include emulsion polymers whose manufacture is described, for example, by Blackley in the monograph "Emulsion Polymerization". The emulsifiers and catalysts which can be used are known per se.

  In principle, it is possible to use elastomers with a homogeneous structure or with a shell structure. The shell-like structure is determined by the order of addition of the individual monomers; the morphology of the polymer is also influenced by this order of addition.

  Only as a representative example of the monomers for producing the rubber part of the elastomer, here, acrylic acids such as n-butyl acrylate and 2-ethylhexyl acrylate, the corresponding methacrylates, butadiene and isoprene, and their A mixture may be mentioned. These monomers can be copolymerized with further monomers such as styrene, acrylonitrile, vinyl ethers, and further acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate.

  The soft or rubber phase of the elastomer (having a glass transition temperature below 0 ° C.) constitutes the core, the outer sheath, or the intermediate shell (for elastomers composed of more than two shells); The shell elastomer may have multiple shells composed of a rubber phase.

  If, in addition to the rubber phase, one or more hard constituents (having a glass transition temperature above 20 ° C.) are involved in the structure of the elastomer, these are generally the major monomers styrene, acrylonitrile, methacrylonitrile, α-. It is prepared by the polymerization of methylstyrene, p-methylstyrene, acrylic and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate. Here too, smaller proportions of further comonomers may additionally be used.

（式中、置換基は以下の意味を有し得る：
Ｒ^１０ 水素又はＣ_１−〜Ｃ_４−アルキル基、
Ｒ^１１ 水素、Ｃ_１−〜Ｃ_８−アルキル基又はアリール基、特にフェニル、
Ｒ^１２ 水素、Ｃ_１−〜Ｃ_１０−アルキル基、Ｃ_６−〜Ｃ_１２−アリール基又は−ＯＲ^１３、
Ｒ^１３ 任意に酸素含有基又は窒素含有基で置換され得るＣ_１−〜Ｃ_８−アルキル基又はＣ_６−〜Ｃ_１２−アリール基、
Ｘ 化学結合、Ｃ_１−〜Ｃ_１０−アルキレン又はＣ_６〜Ｃ_１２−アリーレン基）、
又は

（Ｙ Ｏ−Ｚ又はＮＨ−Ｚ及び
Ｚ Ｃ_１−〜Ｃ_１０−アルキレン又はＣ_６−〜Ｃ_１２−アリーレン基）
のモノマーの併用によって導入され得る官能基も含まれる。 In many cases it has proved to be advantageous to use emulsion polymers having reactive groups on the surface. Examples of such groups include epoxy groups, carboxyl groups, latent carboxyl groups, amino groups or amido groups, and the general formula

Where the substituents can have the following meanings:
R ¹⁰ hydrogen or a C ₁ -to C ₄ -alkyl group,
R ¹¹ hydrogen, a C ₁ -to C ₈ -alkyl or aryl group, especially phenyl,
R ¹² _hydrogen, C 1 _{-~C 10} - alkyl _group, C 6 _{-~C 12} - aryl group, or ^{-OR 13,}
R ^{13 A} C ₁ -to C ₈ -alkyl group or C ₆ -to C ₁₂ -aryl group which may be optionally substituted with an oxygen-containing group or a nitrogen-containing group
X a chemical _bond, C 1 _{-~C 10} - alkylene or _C 6 _{-C 12} - arylene group),
Or

(Y O-Z or NH-Z, and Z C ₁ -~C ₁₀ - alkylene or _C 6 _{-~C 12} - arylene group)
Also included are functional groups that can be introduced by the combined use of the above monomers.

  The grafting monomers described in EP-A 208187 are also suitable for introducing reactive groups at the surface.

  As further examples, acrylamide, methacrylamide, and substituted esters of acrylic acid or methacrylic acid, such as (Nt-butylamino) ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N -Dimethylamino) methyl acrylate and (N, N-diethylamino) ethyl acrylate.

  Further, the particles of the rubber phase may be in a crosslinked state. Examples of crosslinkable monomers include 1,3-butadiene, divinylbenzene, diallylphthalate and dihydrodicyclopentadienyl acrylate, and the compounds described in EP-A50265.

  It is also possible to use so-called graft-linking monomers, ie monomers with two or more polymerizable double bonds which react at different rates during the polymerization. It is preferred to use compounds in which at least one reactive group polymerises at about the same rate as the other monomer, eg the other reactive group (s) polymerizes very slowly. Different polymerization rates result in a certain proportion of unsaturated double bonds in the rubber. When another phase is then grafted onto this type of rubber, at least some of the double bonds present in the rubber react with the grafting monomers to form chemical bonds. That is, the grafted phase has at least some chemical bonding with the graft substrate.

  Examples of such graft-crosslinkable monomers include monomers containing allyl groups, especially allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or Included are the corresponding monoallyl compounds of these dicarboxylic acids. In addition, there are a great many further suitable graft-crosslinking monomers; see for example US Pat. No. 4,148,846 for further details.

  These crosslinkable monomers are generally present in the impact-modifying polymer in a proportion of up to 5.0% by weight, preferably not more than 3.0% by weight, based on the impact-modifying polymer.

Many preferred emulsion polymers are listed below. First, a graft polymer having a core and at least one outer shell and having the following structure is given:

  These graft polymers, especially ABS and / or ASA polymers in an amount of up to 40.0% by weight, optionally mixed with polyethylene terephthalate, preferably up to 40.0% by weight, are used for impact modification of PBT. Is preferred. Corresponding blended products can be obtained under the trademark Ultradur® S (formerly Ultrablend® S from BASF AG).

  Instead of graft polymers with a multi-shell structure, it is also possible to use homogeneous, ie single-shell elastomers made of 1,3-butadiene, isoprene and n-butyl acrylate or their copolymers. . These products can also be prepared by the combined use of crosslinkable monomers or monomers having reactive groups.

  Examples of preferred emulsion polymers are made of n-butyl acrylate- (meth) acrylic acid copolymer, n-butyl acrylate-glycidyl acrylate or n-butyl acrylate-glycidyl methacrylate copolymer, n-butyl acrylate. Graft polymers having an inner core based on styrene or butadiene and an outer coating of the above copolymers, and copolymers of ethylene with comonomers providing reactive groups.

  The elastomers described may also be prepared by other conventional methods, such as suspension polymerization.

  The silicone rubbers described in DE-A 3725576, EP-A 235690, DE-A 3800603 and EP-A 319290 are likewise preferred.

  It will be appreciated that it is also possible to use mixtures of the rubber types mentioned above.

  The production of the thermoplastic molding composition according to the invention and of the mixture for imparting flame-retardant properties is carried out by mixing the raw materials.

  Thermoplastic molding materials are used in the production of moldings, fibers or films and are produced by melting, extruding and subsequently molding the thermoplastic molding material.

  Molded articles are preferably (electrical) switches, plugs, connectors and skeletons for electronic or electrical components.

  The thermoplastic molding materials according to the invention can be manufactured by known methods by mixing the starting components in conventional mixing equipment and then extruding the resulting mixture. Suitable processing machines are described in Handbuch der Kunststofffusion, Volume 1, Grundlagen, Editor F.M. Hensen, W.M. Knappe, H .; Potente, 1989, pp. 3-7 (ISBN3-446-14339-4) and Volume 2, Extrusionsanlagen, 1986 (ISBN3-446-14329-7). After extrusion, the extrudate can be cooled and ground. It is also possible to premix the individual components and to add the remaining starting materials individually and / or likewise in the form of a mixture or as a concentrate in the carrier polymer (masterbatch). The mixing temperature is generally in the range of 230-320 ° C.

  The present invention will be described more specifically by the following examples.

Input material:
A PA66 VZ120 cm ³ / g, Ultramid (registered trademark) A24, BASF SE Polyamide 6 VZ150 cm ³ / g, Ultramid (registered trademark) B27, BASF SE PA6I / 6T Selar (registered trademark) A3426, DuPont B b cyclophosphazene (Registered trademark) FP110, Fushimi Pharmaceutical Co., Ltd. C Aromatic polyphosphate PX-200, Daihachi Chemical Co., Ltd. D Aluminum diethyl phosphinate salt (DEPAL) Exolit (registered trademark) OP1230, Clariant AG E glass fiber OCF DS1110
F Melamine Poly (aluminum phosphate) Safire (R) 400
Melamine polyphosphate (MPP) Melapur® M200, BASF Schweiz (Comparative example only)
processing:
The individual components were mixed in a twin-screw extruder (ZSK25) with a throughput of about 20 kg / h and a flat temperature profile at about 280 ° C. (PA66), extruded, cooled until pelletizable and pelletized. Turned into The test specimens listed in the table were injection molded on an Arburg 420 injection molding machine at a melt temperature of about 260-280 ° C and a molding temperature of about 80 ° C.

  The composition of the molding material and the measurement results are found in the table.

Test implementation:
Mechanical properties were determined according to ISO 527-2 / 1A / 5 and Charpy impact strength (without notch) was determined according to ISO 179-2 / 1eU.

  The flame retardancy of the molding material is first determined according to the method of UL94-V (Underwriters Laboratories Inc. Standard of Safety page, "Test for Flammability of pages 19th, 14th, 18th, 14th, 14th, 14th, 18th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 18th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 18th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 14th, 18th, 14th, 14th, 14th, 14th, 18th, and 14th pages of assemblage of materials as it is available. Were determined.

Glow wire test:
The glow wire test was carried out according to DIN EN60695-2-11 / -12 / -13 (valid version March 2017). According to IEC 60335-1, as a test standard for the component parts (in this case plugs) reported in the examples, it was observed whether flame formation was visible for more than 2 seconds. The temperature reported in the example is the maximum temperature of the glow wire where flame formation did not occur.

  By way of example, a plug, which can be regarded as typical for the relevant product class, was used as a component part in the examples. The plug contains sections of different wall thickness (0.8 mm in thin places, 2 mm in thick places, external dimensions 23 mm x 10 mm x 17 mm). The plug is made of the molding material according to the invention and does not exhibit dark dots.

TGA:
Thermal mass spectrometry was performed using a TA Instruments Q5000IR instrument. The mass of the sample was 2-3 mg. The sample was weighed in an aluminum crucible and the material was heated from 40 ° C to 600 ° C under a stream of nitrogen at a constant heating rate of 20 ° C min ^-1 .

  Example I

  As shown in the examples, the combination of phosphinate, cyclophosphazene and melamine polyphosphate (MPP) passed both the glow wire test of sheets and component parts and the UL94 test with a wall thickness of 0.4 mm. It is possible (Comparative Examples C1 and C2). However, the sample exhibits black planar coloring and black dots. The deep coloration indicates the incompatibility of cyclophosphazene with melamine polyphosphate. Substitution of pure MPP with modified melamine polyphosphate cannot achieve a significant improvement (Comparative Example C3). The small sheet (60 mm × 60 mm × 2 mm) produced by injection molding of the molding material (1) of the present invention and the molding material (C3) not of the present invention has, for example, a uniform light color for the molding material (1). Surface and the molding material (C3) show gray stripes and further gray coloring. A molding material containing a large amount of MPP and cyclophosphazene can achieve very good resistance to glow wire (Comparative Example C4), and because of the effect of MPP as a light-colored filler, it is an attractive material. The surface is brought. However, even a wall thickness of 0.8 mm cannot pass the vertical UL94 test using such samples.

  Next, the formulation containing cyclophosphazene without the addition of MPP fails to pass the glow wire test at 750 ° C (Comparative Example C5). Similarly, the addition of MPP without cyclophosphazene does not pass the glow wire test at 750 ° C (Comparative Example C6). Similarly, even with the reduced addition of the combination of MPP and cyclophosphazene, the glow wire test at 750 ° C. cannot be passed (Comparative Example C7) and a deep tint remains.

  According to the invention, all the requirements of the glow wire and UL94 tests are achieved by the combination of cyclophosphazene, phosphinate and phosphate ester (Examples 1 to 3). The sample exhibits a homogeneous surface with no coloration. The use of the phosphoric acid ester without the addition of cyclophosphazene results in too low a resistance of the molding compound to the glow wire and can only achieve UL94 V1 classification with a wall thickness of 0.4 mm (Comparative Example C8). The molding compositions 1 and 2 according to the invention show not only good flame resistance, but also very good impact strength.

Claims (13)

a) 25.0-64.5% by weight of at least one thermoplastic polyamide as component A,
b) 1.0-10.0 mass% of the general formula (IX) or (X) as component B.

(Wherein, m is an integer of 3 to 25, ^{R 4} and ^{R 4} 'are identical or _{different, C} 1 _{~C 20} - alkyl _{-, C} 6 _{~C 30 -} aryl _{-, C} 6 _{~C 30 -} aryl alkyl -, or _C 6 _{-C 30} - alkyl - represents straight-chain phosphazene substituted aryl or formula (X), n represents 3 to 1000, X is -N = P _{(OPh) 3} or -N = P (O) OPh, Y represents -P (OPh) ₄ or -P (O) (OPh) ₂ ), at least one phosphazene,
c) 1.0-6.0% by weight of at least one aliphatic or aromatic ester of phosphoric acid or polyphosphoric acid as component C,
d) 5.0-30.0% by weight of at least one metal phosphinate or phosphinate of the general formula (I) or of the diphosphinic acid salt of the general formula (II), or polymers thereof, as component D.

(In the formula,
R ¹ and R ² are the same or different and represent hydrogen, linear or branched C ₁ -C ₆ -alkyl, and / or aryl;
R ³ represents a linear or branched _C 1 _{-C 10} - _alkylene, C 6 _{-C 10} - arylene, - alkylarylene or - an aryl alkylene;
M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base;
m = 1-4; n = 1-4; x = 1-4, preferably m = 3, x = 3),
e) 28.0 to 65.0% by weight of glass fibers as component E,
f) 0 to 10.0% by weight of further auxiliaries as component F,
And the total amount of components A to E is 100.0% by mass,
Thermoplastic molding material.   The thermoplastic molding material according to claim 1, wherein a cyclic phenoxyphosphazene having at least three phenoxyphosphazene units is used as the component B.   Thermoplastic molding material according to claim 1 or 2, wherein component C is selected from aromatic polyphosphates. In Component D, R ¹ and R ² are the same or different and represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl, and R ³ is methylene, Ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene, phenylene or naphthylene; methylphenylene, ethylenephenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene or tert-Butylnaphthylene; Thermoplastic molding material according to any one of claims 1 to 3, which represents phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene.   Thermoplastic molding material according to any one of claims 1 to 4, wherein component A is a blend of at least one aliphatic polyamide and at least one semi-aromatic or aromatic polyamide.   Component B is used in an amount of 2.0 to 6.0% by weight, preferably 3.0 to 5.0% by weight, based on the total of components A to E, which add up to 100%. The thermoplastic molding material according to.   2.5-5.5% by weight, preferably 3.0-5.0% by weight, of at least one aliphatic or aromatic ester of phosphoric acid or polyphosphoric acid is used as component C. The thermoplastic molding material according to any one of 1.   A method for producing the thermoplastic molding material according to any one of claims 1 to 7, by mixing the raw materials.   Use of a thermoplastic molding material according to any one of claims 1 to 7 for the production of moldings, fibers or films.   A molded article, fiber or film made of the thermoplastic molding material according to any one of claims 1 to 7.   A method for producing the molded article, fiber or film according to claim 10, by melting, extruding, and then molding the thermoplastic molding material according to any one of claims 1 to 7. 1.0 to 10.0 mass% of the general formula (IX) or (X) as the component B.

(Wherein, m is an integer of 3 to 25, ^{R 4} and ^{R 4} 'are identical or _{different, C} 1 _{~C 20} - alkyl _{-, C} 6 _{~C 30 -} aryl _{-, C} 6 _{~C 30 -} aryl alkyl -, or _C 6 _{-C 30} - alkyl - represents straight-chain phosphazene substituted aryl or formula (X), n represents 3 to 1000, X is -N = P _{(OPh) 3} or -N = P (O) OPh, Y represents -P (OPh) ₄ or -P (O) (OPh) ₂ ), at least one phosphazene,
1.0-6.0% by weight of at least one aliphatic or aromatic ester of phosphoric acid or polyphosphoric acid as component C,
5.0 to 30.0% by weight of at least one metal phosphinate or phosphinate of the general formula (I) or a diphosphinate of the general formula (II), or polymers thereof, as component D.

(In the formula,
R ¹ and R ² are the same or different and represent hydrogen, linear or branched C ₁ -C ₆ -alkyl, and / or aryl;
R ³ represents a linear or branched _C 1 _{-C 10} - _alkylene, C 6 _{-C 10} - arylene, - alkylarylene or - an aryl alkylene;
M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base;
m = 1-4; n = 1-4; x = 1-4, preferably m = 3, x = 3),
Consisting of a mixture.   Use of a mixture according to claim 12 for imparting flame retardant properties to glass fiber reinforced polyamide molding compositions.